Preparation of halogen substituted aminoarylsulphonic acid derivatives



. 2-sulphonic Patented July 22, 1947 PREPARATION OF HALOGEN SUBSTITUTED AMINOARYLSULPHONIC ACID DERIVA- TIVES Henry Martin, Bascl, Hans Heinrich Zaeslin, Riehen, near Basel, and Rudolf Hirt and Alfred Staub, Basel, Switzerland, assignors to J. R. Geigy A. G., Basel, Switzerland No Drawing. Application February 4, 1943, Serial No. 474,730. In Switzerland December 24, 1938 2 Claims. 1 This application is in part a continuation of our application Ser. No. 309,292, filed December 14, 1939, issued August 31, 1943, as Patent No. 2,328,159.

It has been found that new, technically val- 1 liable, water soluble compounds are obtained by treatment of monoaminosulphonic acids of the general formula lNHz I C no H .l 3 in which X represents a divalent atom, such as O or S, or a divalent atomic group, such as S0,

S02, CH2, CO, NH, NH-CO-NH, with aralkylatcan, however, .be partly or wholly introduced into the unhalogenated or low halogenated end prodnot. The position of the halogen atom is immaterial.

In general the following aminosulphonic acids are well adapted for this process: the sulphonic acids of aminodiphenylethers, of aminodiphenylsulphides, of aminodiphenylsulphoxides, of aminodiphenylsulphones, of aminodiphenylmethanes, of aminodiphenylketones, of aminodiphenylamines, of aminodiphenylureae, etc. Particularly advantageous is the use of halogen and alkyl substituted derivatives of th above mentioned amino sulphonic acids, such as for example 4,4-dich1oro-2-amino-l,1'-diphenyletheracid, 4-chloro-4'-amino-l,1'-diphenylether-2 -sulphonic acid, 2' -4-dichloro-4 amino-1,1-dipheny1ether-2-sulphonic acid, 3- methyl-4-chlore-4-amino-1,1-diphenylether-2'- sulphonic acid, 3,4dichloro-4'-amino-1,1-diphenylsulphide-4'-sulphonic acid, 4-chloro-4 .amino- 1, 1 diphenylsulphoxide-Z -sulphonic acid,

4-chlor0-4 amino 1,1 -diphenylsulphone-2 -sulphonic acid, 4,4-dichloro-2-amino-1,1-dipheny1- methane-2-sulphonic acid, 4-chloro-4-amino diphenylketone-3-sulphonic acid, 3,4-dichloro- 4'-aminodiphenylamine-2'-sulphonic acid, etc. Where the unhalogenated aminosulphonic acid is employed, the condensation product is halogenated by the usual process. This can also be employed with products having only a 10W halogen content.

Where halogen substituted aminosulphonic acids are to be used, only selected technically obtainable halogenated compounds are available, as listed above, which, as a consequence of their preparation in a pure form, 1. e. separation from the isomeric or lay-products formed simultaneously during halogenation, are relatively costly. The number ofpossible components is also decreased by the laws of substitution of th halogen atoms.

I'he halogneated aminocliphenylether sulphonic acids have proved themselves, among other monoamino-sulphonic acids as particularly suitable. They are, for example, obtained by condensationof 0. or p-chloronitrobenzene sulphonic acids with halogenophenols and subsequent reduction. The preparation of the halogenated amino-diphenylether sulphonic acids frequently offers certain diificulties, owing to the fact that the manufacture of the intermediate halogenophenols, particularly in the case of the higher substituted halogenophenols, in a pure form is not easy, Thus while pure p-chlorophenol and therefrom the condensation product with ha1ogenonitrobenzenesulphonic acids in a pure form may easily be obtained, on the other hand it is particulary diflicult to manufacture a sumciently pure 2,4-dichlorophenol, as p-chlorophenol and 2,6-dichloropheno1 are invariably present in the technical product owing to the difliculties of separation, as their boiling points are very similar.

As thes products condense similarly and even easier than the-2,4-dichlorophenol, with halogenonitrobenzene sulph'onic acids, so after reduction, is mostly a mixture of halogenated diphenylethers obtained which is not so suitable for a smooth condensation with the mentioned alkylating, aralkylating and acylating agents. Although such mixtures may be suitable for certain technical purposes, for others it is necessary to prefer the homogeneous product. This can be done in part by the halogenation of the already prepared, unhalogenated or only low halogenated amino-arylsulphonic acids prepared according to this invention.

By such halogenation in the usual manners there are, in part, obtained the same aminoarylsulphonic acids as by the use of halogenated components, and, in part, aminoarylsulphonic acids halogenated in other positions, so that by the introduction of different halogens, new, until now technically unobtainable compounds are formed.

For the alkylation, in which only compounds with high molecular alkyl chains are to be used,

cannot only the homogeneous alkyl compounds such as the higher alcohols, prepared, for example, by the reduction of the naturally occurring fats, oils, resins, etc., be used, but also those compounds wh'ose alkyl chains are broken by atoms or molecular-groups, or which are substituted, For example the following are named: chloromethyldodecylether, chloro-methyldodecylthioether, a-halogenocarboxylic acids, or their salts, esters or amides, and particularly the halogenated aromatic amides of (Jr-halogenated aliphatic carboxylic acids.

As aralkylating agents are named: benzylhalogenides, especially however such halogen substituted products as 2-chlorobenzylchloride, 4- chloroor -bromobenzylhalogenides, 3,4-dichlorobenzylchloride, X,X-dichlorobenzylchloride, as obtained by the chlorination of benzyl chloride in presence of iodine, triand tetrachlorobenzyl halogenides etc.

These alkylor aralkyl derivatives of the aromatic aminosulphonic acids can in given cases be further treated with any aliphatic, araliphatic or aromatic acylating agent.

For the acylation of the above mentioned amino-sulphonic acids containing free amino groups, the aliphatic monocarboxylic acids with at least 7 carbon atoms, or any aliphatic polycarboxylic acid or araliphatic or aromatic monoor poly-carboxylic acid can be used. Similarly come into consideration suitable aromatic and araliphatic sulphonic acids. Preferably here also the halogenated derivatives of these compounds are to be used. Obviously it is to be understood that all functional derivatives of the previously mentioned acids such as the esters, halogenides etc., where their use in acylation is known, are also included. As examples are mentioned from the aliphatic carboxylic acids: capric acid, lauric acid, myristic acid, palmitic acid, stearic acid etc., and also the naturally occurring cheap, fatty acid mixtures such as fish-oil acid, palmkernel fatty acid, their derivatives such as halogenopalmkernel fatty acid halogenides, etc. From the araliphatic acylating agents are men tioned: phenylacetic acid, 2- or l-halogenophenylacetic acid, h'ydrooinnamic acid, phenoxyacetic acid, halogensubstituted phenoxyacetic acids, etc. From the aromatic acylating agents: benzoic acid, 2,4- or 3,4-dichlorobenzoic acid, 3,4-dichlorobenzenesulphonic chloride.

The same or similar products can also be prepared from an aromatic monoamine of the forwhere X has the same definition as before, by treatment with the above mentioned alkylating or aralkylating and perhaps acylating agents, followed by sulphonation to produce the solubility in Water.

Through the particular choice of the alkylating, aralkylating and acylating agents or by particular substitution in the aromatic aminosulphonic acids the possibility is given of obtaining products for difierent technical purposes. So can products be obtained which are especially good for the protection of wool, feathers, furs, hair, paper, textiles, leather, natural and artificial fibres, or materials containin these substances, against moths and other textile damaging insects. The fastness to washing, milling and light of such products is noteworthy. By other substitution, alkylation or aralkylation can be prepared products for use as disinfectants, bactericides, fungicides and insecticides, and also particularly good mercury free seed disinfectants. These compounds possess also good penetrative power, which in conjunction with the low poison efiect on humans, makes them especially valuable for technical utilization.

In the instant case, the claims are directed ex clusively to the presently-preferred species of the invention, namely, that involving the aralkylation of 4 amino 4='-amy1-1,1-diphenylether-2-sulphonic acid with 2,3,4,6-tetrachlorobenzylchloride.

The following examples illustrate the invention, the parts being by weight Where nothing other is said.

Example 1 103 parts of nitro-p-chlorobenzylchloride (boiling point 11 mm, 160170 C.), obtained by nitrating p-chlorobenzylchloride, are stirred with 300 parts by volume of chlorobenzene and 100 parts of aluminium chloride at 25 C. until the evolution of hydrochloric acid is complete. The excess of chlorobenzene is distilled with steam after decomposing the aluminium chloride with ice. The residue is extracted with ether, dried and distilled in a vacuum. The condensation product, probably th 2-nitro-4,4'-dichloro-1,1'-diphenylmethane, has the boiling point 15 mm, 220-230 C.

By reduction With iron the 2-amino-4,4-dichloro-1,1'-diphenylmethane is obtained, boiling point 15 mm, 220-230 C. 55 parts of this base are added to 500 parts of sulphuric acid monohydrate and stirred during 2 hours at 100 C., then the whole is cooled, poured on ice, the precipiate filtered off, washed with water and dried. The 2-amino-4A-dichlorol,1-diphenylmethane-2'-sulphonic acid is a white powder with a strongly sweet taste.

17 parts of this diphenylmethanesulphonic acid are dissolved in parts of Water and the solution treated with 30 parts by volume of a 10% soda lye and 12 parts of p-chlorobenzylchloride. The whole is stirred at 90-100 C. until no free amino group is present, which i the case after about 5 hours. Then there is distilled with steam. The condensation product is precipitated from the residual solution as a tough resin by addition of sodium chloride. It is separated OE and after drying is a light colored powder, very soluble in Water.

Example 2 18.5 parts of 4 amino 4'-amyl-1,1'-diphenylether-2-su1phonic acid, obtained by condensation of amylphenol with p chloronitrobenzenesulphonic acid and subsequent reduction, are dissolved in parts of Water and the necessary amount of caustic soda lye, 20 parts of 2,3,4,6-tetrachlorobenzylchloride are added, the whole is boiled for about 24 hours until no free aminosulphonic acid is detectable. The resulting acid is from time to time neutralized with sodium carbonate. The condensation product precipitates in an oily condition and is separated off and dried.

By condensing 4-nitro-1,2-dichlorobenzene with 2-chloro-4-amylphenol, reduction of the nitro compound and subsequent sulphonation according to Example 1, and condensing the so obtained amino compound with 2,3,4,6-tetrachloro-benzylchloride a very similar product is obtained.

Instead of the 4-amino-4-amyl-1,1-diphenylether-Z-sulphonic acid other alkylated diphenylethersulphonic acids may be used, for example ,SOsH (J1 HuOtQOQ-NH-QHQGI c1 c1 c1 01 Example 3 '20 parts of z-amino-l-A dichloro-1,1-diphenyl ether-T-sulphonic acid (made-by smooth sulphonation of 2-amino-4,4"-trichloro-1,1-diphenylether) are dissolved with 12 ,parts 'of chloroacetic acid-3,4-dich1oroani1ide in 100 parts by volume of hot alcohol and mixedwithfi parts of calcinated soda. The whole is boiled under reflux with stirring during 15 ,hours, thendiluted with 300 parts of water andthe separated product filtered off. It is dissolved in hot water, freed from a little insoluble matterpbyfiltering hot and cooled, whereby the condensation productseparates; it is dried in a vacuum, giving a light 001- cred powder, soluble in hot water.

The resulting product has'in salt form the following formula:

Instead of the chloroacetic acid 3;4-'dichloroanilide'other amides of the chloroacetic acid can be employed, "for instance the -chloroanilide, ZA-dichloroanilide, 4-chlorobenzylamicle etc.

Instead of 2-amino-4-A -dichloro-1,1-diphenylether-2'-sulphonic "acid there may be used 4- amino-4',5-dichloro-1,1-diphenylsulphide-2-su1- phonic acid, 2-amino-4;5'-dichloro-.1,1-diphenylsu1phide-4-sulphonic acid, 2-amino-4'-chloro- 1,l-diphenylsulphide-4-sulphonic acid, 4-amino- 3,6-dichloro-1,1-diphenylsulphide-2 sulphonic acid, 2-amino-3,6-dichloro 1,1 diphenylsulphide-l-sulphonic acid, 4-amino-4'-bromo-1,1'- ,diphenylsulphide-2t-su1phonic acid, 2-.amino-4'- 'bromo-i1,1'-diphenylsulphide-4-sulphonic.acid,1:4- iamino -chloro-6'-methyl 1,1 diphenylsul .methoxy-l,1'-diphenylsulphide 2-sulphonic acid,

'2-sulphonic acid, 2-amino-3,4,6'-trichloro-1,1-

diphenylsulphide l-sulphonic acid, 4=-amino-2',4'- dichloro-1,l'ediphenylsulphide-2-sulphonic acid or 2-amino-2f,4'-dichloro-1,1-diphenylsulphide- -sulphonic acid. These compounds can also be madeby'the above mentioned method.

6 The-product made by condensation of amino- 4-ehlorc -1,1 -diphenylsulphide-2 sulphonic acid with 2,4,6-trich1orobenzylchloride according to this example is a readily soluble powder of sim-llartproperties.

Example 4 10 parts of d am-inol'-chloro 5 -methyl-l,l diphenyIether-Z -sulphonic acid are suspendedin 100'partsby volume-oi benzene, 8 parts of chloromethyhdodecyletherare added and the whole is boiled. Therresulting acid is graduallyineutralized'with 5 parts of potassium carbonate. When a test showsno free amine, the-precipitated prodnet is isolated and'dried in :a vacuum.

Instead 'of the chloromethyl-dodecy1ether: there may be used the chloromethyldodecylthioether.

.Emmple, 5

25.4 parts of "4:131'1'111105',5"'di-Qh1QI'O]-,1"diphenylether, made by condensation of 4,5-dichlorophenol with 4-chloronitrobenzenea andwsubsequent :reduction,-are heated with 27 parts of dodecylbromide (orequimolecular parts of decyl or Lmyris'tylbromide) during .13 hours to .160-170 C., then .i'or a further .15 hOIlZSEtO 170-4180" until .no more .hydrobromic acid escapes and a test showsnnofreeamine. The cold 'melt isdirectly sulphonated. ,It. iszdissolved in-4003partsof sulphuridacid monohydrateand heated to ,90" C. until' a test is: soluble to: a. clear-solution inssodium carbonate. Assoon as this is the caseath-e mass is :nouredvon ice; some resin filtered off, the. solutionStreated-pwith :animal charcoal, filtered, and saltedout. The sulphonic acidsaltsgareobtained by neutralization.

The sulphonic acidmay-be acylatedby 'treatment with propionicor butyric acid :anhydride;

asimilar compoundis obtained by acylatingthe neutralized with diluted caustic soda lye.

unsulphonated compound and I sulphonating afterwar'ds.

Instead of the 4. -amino-4,5-dich1oro-1,1"wdiphenylether there may also be used other unsuiphonated compounds, for example 4amino-4- chlorow-l,1-diphenylether, 4-amino-e4'-ch1oro-5' methyl- 1,1 -diphenylether, 4-amino-2A' -dich1o ro 1,1 --diphenylether, 2 amino 4,4'-dichloro-5' -:methyl-1,1 diphenylether, 4-amino1-2A dichloro-fi'-methyl-1,1-dipheny1ether, 2-amino- 4,4',5'etrichloro-Ll-dihpenylether, 4-ami n o- 2;4,5'-trichloro-1,1 diphenylether, 2a m i n;o 4,2 -dichloro-1,l "-diphenylether, ,4-amino-4' ,6' dichloro-1,1'-dipheny1ether, 2-amino-4,4,6'-trich1oro-1,1-diphenylether, 2-amino-4',6'-dichloro-1;1--diphenylether, .2-amino-4A',fi-trichloro- 5 methyl-1,1 -diphenylether, 2-amino-4,4 ,5-trichloro-il ,1, diphenylether, .2-amino -4-ch1oro-4' amyl-1,1 -diphenylethen or l-amino-Z-chloro-l- -amyl-1,1-diphenylether. In -each case the sulphonation can be performed before or'after the alkylation.

' Example 6.

19.5 parts of 2-amino-2Q4';5-=trich1oro 1,1- diphenylethewi-sulphonic acid are dissolved in 150 parts of water with the necessary quantity of sodium carbonate, 8 parts of p-chlorobenzylchloi ride are added and the whole is heated to 70-80 C. until-no free'amino group is detectable. The hydrochloric acid formed is from time-to time The "separated resin-is filtered off and dried in a vacuum. 1G parts of this condensation product are armedonawaterbath'for 2 "hours with parts by volume of acetic acid 'anhydride, then the whole is poured into water and after decomposing the excess of anhydride filtered off, washed with a: sodium chloride solution and dried in a vacuum.

Similar compounds are obtained with tetrachlorobenzylchloride instead of the monohalogen compound and by using acetic, propionic or butyric acid anhydride as acylating agents,

Instead of the 2 -amino-2',4',5-trichIoro-1,1'- diphenylether-4-sulphonic acid also the 4-amino- 4'-amyl-6'-chloro-1,1'-diphenylether-2-sulphonic acid, 4-amino-2',4,5-trichloro-1,1-diphenylether-2-sulphonic acid, 2-amino-4',5-dichloro- 1,1'-diphenylether-4-sulphonic acid, 2-amino- 4',5-dicl'iloro-5-methyl- 1,1 diphenylether 4 sulphonic acid, 4-amino-2-chloro-1,1-diphenylether-2-sulphonic acid, 4-amino-4,6'-dichloro- 1,1-diphenylether-2-sulphonic acid, 2-amino- 4',6'-dichloro 1,1'- diphenylether 4 sulphonic acid, 4-amino-4'-chloro-1,1-diphenylether-2- sulphonic acid, 2-amino-4-chloro-1,1-diphenylether-4-sulphonic acid, 2-amino-4'chloro-5'- methyl-1,1-diphenylether-4-sulphonic acid, 4- amino-4',5'-dichloro1,1-diphenylether 2 sulphonic acid, 4-amino-4-chloro-3,5'-dimethy1- 1,1'-diphenylether-2-sulphonic acid, 2-amino-4'- chloro-'3',5-dimethyl 1,1'- diphenylether-4-sulphonic acid, 4-amino-4'-chloro-3'-methyl-6'-isopropyl-1,1'-diphenylether-Z-sulphonic acid, 2- amino-4'-chl0ro-3'-methyl-6-isopropyl-1,1'-di phenylether-4-sulphonic acid, 2-amino-3',6'-dichloro-1,1-diphenylether-4-sulphonic acid, 4- amino-3,6'-dich1oro-1,1'-diphenylether 2 sulphonic acid, or the 2-amino-4'-amyl-6'-chloro- 1,1'-diphenylether-4-sulphonic acid may be used. These diphenylether sulphonic acids are obtained according to known processes by condensing or p-chloronitrobenzene sulphonic acids with the corresponding phenols and subsequent reduction.

Also the sulphonated compounds of the list of Example 5 may be used as well. In addition are also available for instance 4amino-4,5'-dichloro-1,1'-diphenylamine-2-sulphonic acid, 4- a min 0 4'-chloro-1,1-diphenylsulph0neor -sulphoxide-2-sulphonic acid, made by reacting sodium 4-chlorophenylsulphonate with sodium 4-nitrochlorobenzene-2-sulphonate or by reacting 4-chlorothiopheno1 with sodium 4-nitrochlorobenzene-2-sulphonate and oxidizing with H202, the unoxidized thioether itself, 2-amino-4,4- -dichloro-l,1'-diphenyl-urea-2'-su1phonic acid, 4-

chloro-4 -aminodiphenylketone-3-sulphonic acid.

Example 7 brownish mass.

Example 8 72 parts of the benzylderivative according to Example '7 are well comminuted, intermixed with 400 parts by volume of acetic acid anhydride and heated to boiling for 6 hours on the reflux apparatus. Then the reaction mass is poured into water to destroy the unaltered acetic acid anhydride, the precipitated acetylderivative. is removed by suction and dried. It constitutes a powder.

15 parts of the said acetylderivative are dissolved in 300 parts by volume of water and chlorine is slowly passed therethrough at ordinary temperature. After about 2 hours there is neutralized with a sodium carbonate solution and salted out, whereby the chlorinated product precipitates out as semi-solid mass.

But it is also possible to brominate as follows:

30 parts of the above halogen-free acetylderivative are dissolved in 600 parts by volume of water and. 12 parts of bromine are then dropped in at ordinary temperature; after stirring for 2 hours there is neutralized with a sodium carbonate solution and the product is saltedout. The brominated product precipitates out as semi-solid mass, which solidifies after some time.

Instead of the above mentioned aminoarylsulphonic acid derivatives there may be used also the numerous other compounds listed in the description and the Examples 1-8 and also their basic compounds containing fewer halogen atoms or no halogen at all.

The improved products can f. i. be used for the treatment of textiles to render them moth-proof. Such treatment can be carried out as follows:

(a) Wool or wool containing fabrics are treated at boiling temperature for 45 minutes to 1 hour with a solution of 0.3 to 0.6% of one of the compounds according to Examples 1 to 8 (calculated on wool), 3 to 5% of sulphuric acid and 10% of crystalline Glaubers salt, then the goods are rinsed and dried, or

(b) Wool is treated at 60" C. for 45 minutes with a solution of 0.3 to 0.6% of the above mentioned compounds and 10 to 20% of crystalline Glaubers salt, then it is rinsed and dried.

What we claim is:

1. A process for the manufacture of a halogen substituted aminoarylsulphonic acid, comprising aralkylating 4-amino 4'- amyl 1,1- diphenylether-Z-sulphom'c acid by reacting the same with 2,3,4,6-tetrachlorobenzylchloride.

2. The halogen substituted amino-arylsulphonic acid of the formula HENRY MARTIN.

HANS HEINRICH ZAESLIN. RUDOLF HIRT.

ALFRED STAUB.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,012,853 Holste Dec. 26, 1911 1,766,952 Saunders June 24, 1930 1,841,636 Saunders Jan. 19, 1932 1,917,441 Fischer July 11, 1933 2,022,889 Lauer Dec. 3, 1935 2,158,407 Conzetti May 16, 1939 1,898,457 Muth Feb. 21, 1933 FOREIGN PATENTS Number Country Date 333,559 Great Britain 1930 

